Lubricant addition agents and lubricants containing same



States This invention relates to novel compositions of matter which areeffective as multi-function addition agents in lubricant compositions.More particularly, this invention pertains to improved lubricantcompositions containing novel oil-soluble barium-containing neutralizedphosphorus sulfide-hydrocarbon reactions having the ability to improvedetergency and rust inhibition properties of a lubricating oil.

Within recent years, it has become common practice to impart theimproved properties to lubricants through the use of various types ofaddition agents. Lubricating oils employed in internal combustionengines, such as spark ignition and diesel engines generally require theuse of more than one addition agent to improve the serviceability of thelubricating oil under conditions of operation of the engine. Because theconditions of operation of an engine are such as to require manydifferent types of improvement in a lubricating oil, many differenttypes of additives are employed. Among the more important additiveemployed, it is the type which functions to prevent the formation andaccumulation of sludge and varnish deposits and coatings on cylinder andpiston walls of engines. Such addition agents have the property ofmaintaining clean engines and are referred to as detergent type additionagents. Such detergent type addition agents generally must be effectiveunder heavy duty, high temperature conditions of engine operation. It isdesirable to provide detergency addition agents for such conditions.

In recent years, the use of neutralized phosphorus sulfide-hydrocarbonreaction products as detergency lubricant addition agents has becomemore and more prominent. Higher basic metal content in such neutralizedproducts is desirable in that it results in a corresponding increase indetergency properties of the product. In creased detergency isparticularly valuable in recent years as more advanced engine designsnecessitate the use of higher detergency lubricants. Further, modernengines require other addition agents in larger amounts and eachadditional amount of addition agent added to the lubricant replaceslubricating oil in the lubricant and the lubricating ability of thelubricant is correspondingly decreased. Thus, it is desirable toincrease the basic metal content and detergency properties of thedetergency addition agent so that the same amount of more detergency maybe obtained from a smaller amount of addition agent.

Further, when neutralizing such products with barium, in processes forpreparing such addition agents, many problems in handling the reactantsand reaction product have been incurred. Often in such neutralizations,the product is difficult to filter and has a hazy appearance, detractingfrom its commercial acceptability.

We have provided certain new and useful oil-soluble neutralizedphosphorus sulfide-hydrocarbon reaction product complexes for use asmulti-purpose addition agents in lubricantsJ The addition agents of thisinvention are easily filtered and clear in appearance and are useful asmulti-purpose addition agents in lubricating oils in amounts from about.002 to about weight percent for the purpose of imparting detergency tothe lubricating oil. The addition agents of this invention are also3,086,940 Patented Apr. 23, 1963 effective in imparting rust inhibitionproperties to the lubricating oil. The process for preparation of thereaction product complexes eliminates hazy appearance in the finalproduct. The additive complexes of this invention are formed byneutralizing a hydrolyzed phosphorus sulfide-hydrocarbon reactionproduct with an excess of an inorganic basic alkali metal or alkalineearth metal compound in the presence of boric acid and a petroleumsulfonic acid. The neutralization is carried out using analcohol-containing reaction solvent for the neutralization reactionmixture.

The basic neutralization reagent, i.e. the inorganic basic alkali metalor alkaline earth metal compound, may be inorganic basic compound of ametal selected from the group consisting of the alkali metals andalkaline earth metals. The inorganic basic alkali metal or alkalineearth metal compound will hereinafter be referred to for convenience asinorganic basic compound. Advantageously the inorganic basic compound isan oxide, hydroxide, carbonate, sulfide, or the like of lithium, sodium,potassium, calcium, barium, strontium, etc. Examples are barium oxide,barium sulfide, barium carbonate, calcium carbonate, calcium oxide,calcium sulfide, potassium hydroxide, sodium bicarbonate, sodiumsulfide, sodium hydroxide, lithium hydroxide, lithium sultide, strontiumoxide, etc. Barium oxide is particularly preferred.

The alcohol reaction solvent may be any aliphatic alcohol boiling belowabout 350 F. or mixture of such alcohol with water. More advantageouslythe aliphatic alcohol is a saturated aliphatic alcohol having from 1 toabout 7 carbon atoms. Methanol is particularly preferred. Where amixture of alcohol and water is used as the alcohol reaction solvent,the water may be present in amounts up to about 2.0 mols, advantageouslyat least about .05 mol, and preferably from about 0.5 mol to about -1.5mols per mol of basic alkali or alkaline earth compound. Examples ofsuitable aliphatic alcohols are methanol, ethanol, isopropanol, butanol,pentenol, pentanol, methyl-butyl alcohol, hexanol, hexenol,cyclohexanol, ethylhexyl alcohol, octyl alcohol, and the like. Thealcohol reaction solvent is used during reaction with excess inorganicbasic compound in amounts sufficient to provide from about 2 to about 15mols of aliphatic alcohol per mol of inorganic basic compound andpreferably from about 3 to about 7 mols per mol of inorganic basiccompound.

The neutralization is carried out by reacting the inorganic basiccompound, the hydrolyzed phosphorus sulfide-hydrocarbon reactionproduct, boric acid, and the petroleum sulfonic acid in admixture at atemperature in a range from about F. to about 400 F. and preferably fromabout F. to about 200 F. It is advantageous to carry the reaction out ator below the reflux temperature of the alcohol-containing reactionsolvent since the reaction temperature can thereby be more easilycontrolled. The neutralization with the inorganic basic compound forms aneutralized product having a high ratio of alkali metal or alkalineearth metal to phosphorus. It is preferred to use from about 1.5 toabout 4.0 mols of inorganic basic compound per mol of phosphorus in thehydrolyzed phosphorus sulfide-hydrocarbon reaction product in thereaction mixture although any amount of from about 0.8 to about 5.0 ormore mols of inorganic basic compound per mol of phosphorus may be used.Preferably, the inorganic basic compound is added to the reactionmixture as a slurry in a diluent mineral oil or water or other diluent.

The neutralization reaction is carried out in the presence of thealcohol-containing reaction solvent, the boric acid, and the petroleumsulfonic acid until neutralization is complete. After the neutralizationwith barium oxide, the resulting product is filtered to remove solidmaterials such as unreacted inorganic basic compound or inorganic saltsthereof; filtration may be easily accomplished by diluting the productwith a mineral lubricating oil and heating the diluted product to atemperature in the range of from about 200 to about 400 F. andpreferably about 350 F. and then filtering the heated diluted productthrough an absorbent material such as silica gel, Celite, Attapulgusclay, fullers earth, and the like.

As the preferred procedure, the alcohol-containing reaction solvent, theboric acid, and the petroleum sulfonic acid are heated to reactiontemperature before addition of the inorganic basic compound forneutralization. Other procedures will be obvious to those skilled in theart. However, in any procedure, the hydrolyzed phosphorussulfide-hydrocarbon reaction product should not be permitted to reactsubstantially with the inorganic basic compound before addition of theboric acid and petroleum sulfonic acid. In the preferred embodiment, theboric and sulfonic acids are added before the inorganic basic compoundor alternatively after or at the same time as the inorganic basiccompound but before the reaction mixture is heated to reactiontemperature.

The hydrolyzed phosphorus sulfide-hydrocarbon reaction product may beprepared by reacting a normally liquid hydrocarbon with a phosphorussulfide, such as P S P S P 8 or other phosphorus sulfides, andpreferably phosphorus pentasulfide, P S and hydrolyzing the resultingproduct.

The normally liquid hydrocarbon constituent of this reaction is suitablya high boiling hydrocarbon such as is described in detail in U.S.2,316,080, 2,316,082, and 2,316,088, each issued to Loane et al. onApril 6, 1943. While the hydrocarbon constituent of this reaction can beany of the type hereinafter described, it is preferably amono-olefinhydrocarbon polymer resulting from the polymerization of low molecularweight mono-olefinic hydrocarbons or isomono-olefinic hydrocarbons, suchas butylenes, or the copolymers obtained by the polymerization ofhydrocarbon mixtures containing isomonoolefins and mono-olefins ormixtures of olefins in the presence of a catalyst, such as sulfuricacid, phosphoric acid, boron fluoride, aluminum chloride or othersimilar halide catalysts of the Friedel-Crafts type.

The polymers employed are preferably mono-olefin polymers or mixtures ofmono-olefin polymers and isomono-olefin polymers having molecularweights ranging from about 150 to about 50,000 or more, and preferablyfrom about 300 to about 10,000. Such polymers can be obtained, forexample, by the polymerization in the, liquid phase of a hydrocarbonmixture containing monoolefins and isomono-olefins such as butylene andisobutylene at a temperature of from about 80 F. to about 100 F. in thepresence of a metal halide catalyst of the Friedel-Crafts types such as,for example, boron fluoride, alumina chloride, and the like. In thepreparation of these polymers we may employ, for example, a hydrocarbonmixture containing isobutylene, butylenes and butanes recovered frompetroleum-gases, especially those gases produced in the cracking ofpetroleum oils in the manufacture of gasoline.

Essentially parafinic hydrocarbons such as bright stock residuums,lubricating oil distillates, petrolatums, or paraffin waxes, may beused. There can also be employed the condensation products of any of theforegoing hydrocarbons, usually through first halogenating thehydrocarbons, with aromatic hydrocarbons in the presence of anhydrousinorganic halides, such as aluminum chloride, zinc chloride, boronfluoride, and the like.

Other preferred olefins suitable for the preparation of the hereindescribed phosphorus sulfide reaction products are olefins having atleast 20 carbon atoms in the molecule of which from about 13 carbonatoms to about 18 to I. W. Gaynor et al. on April 6, 1943.

carbon atoms, and preferably at least 15 carbon atoms, are in a longchain. Such olefins can be obtained by the dehydrogenation of parafiins,such as by the cracking of paraifin waxes or by the dehalogenation ofalkyl halides, preferably long chainalkyl halides, particularlyhalogenated parafiin waxes.

The phosphorus sulfide-hydrocarbon reaction product is prepared byreacting the phosphorus sulfide, e.g. P 5 with the hydrocarbon at atemperature of from about 200 F. to about 600 F., preferably from about300 F. to about 500 B, using from 1% to about 50%, preferably from about5% to about 25% of phosphorus sulfide; the reaction is carried out infrom about one to about ten hours. It is preferable to use an amount ofthe phosphorus sulfide that will-completely react with the hydrocarbonso that no further purification is necessary; however, an excess of thephosphorus sulfide can be used, and the unreacted material separated byfiltration. The reaction, if desired, can be carried out in the presenceof a sulfurizing agent such as sulfur or a halide of sulfur as describedin US. 2,316,087, issued It is advantageous to maintain a non-oxidizingatmosphere, for example an atmosphere of nitrogen, in the reactionvessel. The reaction product obtained is then hydrolyzed at atemperature of from about 200 F. to about 500 F., preferably at atemperature of about 300 F .400 F. by suitable means, such as forexample, by introducing steam through the reaction mass. The hydrolyzedprod not, containing inorganic phosphorus acids formed during thehydrolysis can beused as such in the subsequent neutralization stage; orit can be substantially freed of the inorganic phosphorus acids bycontacting with an adsorbent material such as Attapulgus clay, fullersearth and the like at a temperature of F.500 F. as fully described andclaimed in US. 2,688,412, issued to R. Watson on Septemper 7, 1954, orby extraction with phenol or an alkanol of 1 to 5 carbon atoms inadmixture with water as described and claimed in US. 2,843,579, issuedto N. E. Lemmon et al. on July 15, 1958.

The boric acid is used in the neutralization reaction mixture in amountsof from about 0.1 to about 5.0 mols and preferably from about 0.5 toabout 2.5 mols per mol of phosphorus in the hydrolyzed phosphorussulfidehydrocarbon reaction product. The boric acid may be added asboric acid or may be prepared in situ in the reaction mixture by addingboric acid anhydride or a boric acid ester which is capable ofdecomposition to give boric acid in the reaction mixture, for example,by dissociation upon heating or by dissociation through bydrolysis orother means. i

The petroleum sulfonic acid is present in the neutralization reactionmixture in amounts of from about 1 to about 30 parts by weight andpreferably from about 4 to about 15 parts by weight per part by weightof phosphorus present in the hydrolyzed phosphorus sulfide-hydrocarbonreaction product.

The petroleum sulfonic acids are those sulfonic acids produced in theacid treatment of petroleum mineral oil fractions such as minerallubricating oil fractions with such agents as sulfuric acids orchloro-sulfonic acids. The petroleum sulfonic acids are well known inthe art. Such petroleum sulfonic acids normally contain sulfonatedaromatic constituents. They can be obtained, for example, by treatingany normally liquid petroleum fraction which contains aromatichydrocarbons with concentrated sulfuric acid (or sulfur trioxide). Amore particular petroleum sulfonic acid which is usable in thisinvention is the petroleum sulfonic acid obtained by sulfonating anaromatics containing solvent extract from an SAE 40 lubricating oil.Such sulfonation can be effected by treating the extract with sulfurtrioxide or concentrated sulfuric acid. Petroleum sulfonic acidsgenerally have a molecular weight within the range of from about 400 toabout 700. The sulfonic acids contemplated herein are preferentiallyoil-soluble and are commonly called mahogany acids as distinguished fromthe water soluble green acids. Although the green acids are notacceptable when used alone, in forming the reaction product of theinvention, they may sometimes be used in admixture with the mahoganyacids with acceptable results. Sulfonation of an aromatics containingfraction produces a sulfonic acid-containing composition known in theart as sour oil. Although the sulfonic acids are normally extracted fromsour oil before its use in the industry, in the process of the presentinvention the sour oil is preferably used directly, without extraction,as the sulfonic acid component in the reaction for convenience andelimination of the necessity for extraction.

Although we do not Wish to be held to any theories regarding thereaction, we believe that the addition of boric acid and petroleumsulfonic acid to the barium neutralization reaction mixture causes acomplex of such components with the hydrolyzed phosphorous sulfidehydrocarbon reaction product to form. The complex, in turn, reacts withexcess barium oxide to form the lubricant addition agents of thisinvention.

The following examples are included as illustrations of the preparationof reaction products of this invention and are not intended as limitingour invention.

PREPARATION: HYDROLYZED PHOSPHORUS SULFIDE-HYDROCARBON REACTION PRODUCTAs an illustration of the preparation of the hydrolyzed phosphorussulfide-hydrocarbon reaction product used as an intermediate in thepreparation of addition agents of this invention, a butene polymerhaving an average molecular weight in the range of about 750 to 800 wasreacted with 15.5 wt. percent P 8 at a temperature of about 450 F. for aperiod of about 5 /2 hours. The product was then hydrolyzed with steamat a temperature of about 340 F. until the acidity of the productremained substantially constant with continued steaming. The reactionproduct was diluted with a solvent extracted SAE 5 min eral lubricationoil to a phosphorus content of one mol per 900 grams.

Example I 900 grams of the hydrolyzed phosphorus sulfide-polybutenereaction product of the above preparation, 75 grams of boric acid and 55grams of sour oil (containing 23% preferentially oil-soluble 600 averagemolecular weight petroleum sulfonic acid) were diluted with 300 grams ofa Mid-Continent solvent extracted weight mineral oil. 700 cc. ofmethanol and 20 cc. of water were added to the mixture and the mixturewas heated at the reflux temperature of the methanol and water mixture(160 F.) for 2 hours. An oil slurry of 490 grams of barium oxide in 490grams 5 weight oil was then added to the reaction mixture. Afteraddition of the barium oxide, the mixture was heated at 160 F. for 2hours. The temperature of the reaction mixture was then increased to 350F. and the product was filtered. The filtered product contained 13.55%barium, 108% phosphorus, 0.75% sulfur, and 0.32% boron. The product hada barium to phosphorous weight ratio of 12.54: 1.

Example 11 The hydrolyzed phosphorus sulfide-polybutene reaction productof the above preparation was further diluted with a solvent extractedSAE 5 mineral lubricating oii to a phosphorus content of one mol per1220 grams. 610 grams of the resulting diluted product, 2070 grams ofsour oil (0.75 mol of preferentially oil-soluble sulfonic acid ofaverage molecular weight of about 600) and 80 grams of boric acid werepretreated with 33 cc. H 0 and 650 cc. methanol for two hours at 160 F.(methanol reflux temperature). The resulting pretreated mixture was thenneutralized wtih a slurry of 400 g. of barium oxide in 320 g. of solventextracted SAE 5 mineral lubricating oil 6 at about 160 F. for about twohours. The resulting product was heated to 350 F. and filtered. Thefiltered product contained 8.4% barium, 0.46% phosphorus, 0.3% boron and1.6% sulfur.

The composition of this invention was tested as an addition agent in alubrication oil in accordance wit the procedure of the L-l test, havingCRC designation L-1-545 as fully described in CRC handbook, 1956edition, Co-ordinating Research Counsel, New York. Briefly, the test isconducted in a lA-Sl single cylinder Caterpillar engine operating at1000 rpm. at a load of 19.8 B.H.P. within an oil temperature of to F.and a water jacket outlet temperature of about to F. The test was runfor 480 hours with inspections at the end of 240 and 480 hour periodsfor carbon in the ring grooves, expressed in terms of percent filling ofthe top ring groove with carbon. The sample (designated sample A) testedwas formulated by adding 2.5% of the product prepared in Example I toSAE 30 mineral lubricating oil containing 1% of zinc dialkyl 1dithiophosphate and a polyisobutylene polymer viscosity index improverand having a viscosity index of about 62 sec. at 210 F. For comparisonpurposes a mixture (designated sample B) of components was alsosubjected to the L-l :test procedure. The mixture consisted of the abovebase lubricating oil containing 2.5% of a barium-cont-aining alkalinedetergent (barium:phosphorus weight ratio of 9: 1) prepared byneutralizing a hydroyzed phosphorus sulfide-butene polymer reactionproduct with bari um oxide in the presence of methanol and water atabout methanol reflux temperature and also containing 1% of acalcium-borate-sulfonate prepared by neutralizing a sulfonic acid withcalcium in the presence of boric acid. The results of the L-1 test arereported below. More than 25% filling of the first ring groove isconsidered failing.

TABLE [Caterpillar L-l, S-1 test results] 1 Discontinued after failingat 240 hours.

The data of the above L-l test as reported in the table demonstrateimproved detergency properties of the compositions of this invention. Itis believed that the improved detergency is due to the increased bariumcontent of the compositions, expressed as a barium to phosphorus ratio.Each of samples A and B had the same amount of phosphorus in theneutralized phosphorus sulfide-hydrocarbon reaction product. The datademonstrate that a mixture of ingredients does not give the improveddetergency as the complexed reaction products of our invention.

The herein described additive compositions of the present invention canbe used as indicated above in varying amounts of from .002 up to about25% in lubricating oils. Although the present invention has beenillustrated by the use of the additive compositions in minerallubricating oils, it is not restricted thereto. Other lubricating oilbases can be used, such as hydrocarbon oils, both natural and syntheticfor example, those obtained by the polymerization of olefins, as well assynthetic lubricating oils of the alkylene oxide type and thepolycarboxylic acid ester type, such as the oil soluble esters of adipicacid, :sebacic acid, azelaic acid, etc. It is also contemplated thatvarious other well known additives, such as viscosity index improvers,anti-foaming agents, pourpoint depres- Alkyl groups derived from amixture of 70 mol percent of 'islzorliropyl alcohol and 30 mol percentof the mixed deeyl a co 10 s.

sors, extreme pressure agents, and the like, may be incorporated inlubricating oils containing the additives of our invention.

Concentrates of a suitable oil base containing more than 15 percent, forexample up to 50 percent or more, of the additives of this inventionalone or in combination with other additives can be used for blendingwith hydrocarbon oils or other normally liquid lubricating oils in theproportions desired for the particular conditions of use to give afinished lubricating product containing the additives of this invention.

Unless otherwise stated, the percentages given herein and in the claimsare percentages by weight.

Although was have described our invention by reference to specificembodiments and examples thereof, such specific embodiments and examplesas have been given are merely for the purpose of illustration of theinvention and are not intended as limiting its scope. It is intendedthat modifications and variations of the present invention which areapparent from our foregoing description to those skilled in the art areto be considered within the scope of our present invention.

We claim:

=1. As a new composition of matter, an oil-soluble detergent neutralizedreaction product prepared by the process comprising reacting a normallyliquid hydrocarbon with from about 1% to about 50% of a phosphorussulfide at a temperature in the range of from about 200 F. to about 600R, hydrolyzing the resulting reaction product at a temperature in therange of from about 200 F. to about 500 F., reacting the resultinghydrolyzed reaction product with Irom about 0.1 to about 5.0 mols ofboric acid per mol of phosphorus in said reaction product, from about 1to about 30 parts by weight of petroleum sulfonic acid per part byweight of phosphorus in said reaction product and from about 0.8 toabout 5 .0 mols of an inorganic basic compound per mol of phosphorus insaid reaction product at a temperature in the range of from about 120 F.to about 400 -F. in the presence of an alcoholcontaining solvent whereinthe alcohol is an aliphatic alcohol boiling below about 350 B, saidinorganic basic compound being selected from the inorganic basiccompounds of alkali metals and the inorganic basic compounds of alkalineearth metals and said alcohol-containing solvent providing from about 2to about mols of aliphatic alcohol per mol of inorganic basic compound.

2. The composition of claim 1 in which said boric acid is obtained insitu by dissociation of a boric acid ester.

3. The composition of claim 1 in which said petroleum sulfonic acid is asour oil obtained from the sulfuric acid treatment of a petroleumlubricating oil fraction.

4. As a new composition of matter, an oil soluble detergent-typeneutralized reaction product prepared by the process comprising reactinga normally liquid hydrocarbon with from about 1% to about 50% of aphosphorus sulfide at a temperature in the range of from about 200 F. toabout 600 F., hydrolyzing the reaction product at a temperature in therange of from about 200 F. to about 500 F., reacting the resultingreaction product with from about 0.1 to about 5.0 mols of boric acid permol of phosphorus in said reaction product, and from about 1 to aboutparts by weight of petroleum sulfonic acid per part by weight ofphosphorus in said reaction product at a temperature in the range offrom about 120 F. to about 400 F. in the presence of analcohol-containing reaction solvent wherein the alcohol is an aliphaticalcohol having from 1 to 7 carbon atoms, and reacting the resultingreaction mixture with from about 0.8 to about 5.0 mols of an inorganicbasic compound of a metal selected from alkali metals and alkaline earthmetals per mol of phosphorus in said reaction product at a temperaturein the range of from about 120 F. to about 400 F. in the presence ofsaid reaction solvent, said reaction solvent being present in thereaction mixture in an amount sufficent to provide from about 2 to about15 mols of said aliphatic alcohol per mol of inorganic basic compound.

5. The composition of claim 4 wherein said normally liquid hydrocarbonis a butene polymer having a molecular weight of from about 150 to about50,000.

6'. As a new composition of matter an oil soluble detergent neutralizedreaction product prepared by the process comprising reacting a normallyliquid hydrocarbon with from about 1% to about 50% of a phosphorussulfide at a temperature in the range from about 200 F. to about 600 F.,hydrolyzing the reaction product at a temperature in the range of fromabout 200 F. to about 500 F., heating the resulting reaction product inthe presence of from about 0.5 to about 2.5 moles of boric acid per moleof phosphorus in said reaction product, from about 4 to about 15 partsby Weight of a petroleum sulfonic acid per part by Weight of phosphorusin said reaction product and a solvent selected from methanol and amixture of methanol and water at a temperature in the range from about140 F. to about 200 F., neutralizing the resulting heated mixture withfrom about 1.5 to about 4.0 mols of barium oxide per mol of phosphorusin said reaction product at a temperature in the range of from about 140to about 200 P., in the presence of said reaction solvent, said reactionsolvent being present in the reaction mixture in an amount suflicient toprovide from about 2 to about 15 mols of methanol per mol of bariumoxide, and filtering the resulting neutralized product to removeinorganic contaminants therefrom.

7. A lubricant composition comprising a major proportion of a normallyliquid lubricating oil and from about .002 to about 25% of thecomposition of claim 1.

8. A lubricant composition comprising a major pro portion of a normallyliquid lubricating oil of from about .002 to about 25% of thecomposition of claim 4.

9. An addition agent concentrate for lubricating oils consistingessentially of a lubricating oil containing more than about 15% of theoil soluble neutralized reaction product of claim 1, said concentratebeing capable of dilution with a normally liquid lubricating oil to aconcentration of said reaction product in the range of from about .002to about 25 10. An addition agent concentrate for lubricating oilsconsisting essentially of a lubricating oil containing more than about15% of the oil soluble neutralized reaction product of claim 4, saidconcentrate being capable of dilution with a normally liquid lubricatingoil to a concentration of said reaction product in the range of fromabout .002 to about 25 11. A process for making new and usefuloil-soluble detergent neutralized phosphorus sulfide-hydrocarbonreaction products, which process comprises reacting a hydrolyzedphosphorus sulfide-hydrocarbon reaction product, said hydrolyzed producthaving been prepared by reacting a normally liquid hydrocarbon with fromabout 1% to about 50% of a phosphorus sulfide at a temperature in therange of from about 200 to about 600 F and hydrolyzing at a temperaturein the range of from about 200 to about 500 F., with from about 0.1 toabout 5.0 mols of boric acid per mol of phosphorus in said reactionproduct, from about 1 to about 30 parts by weight of petroleum sulfonicacid per part by weight of phosphorus in said reaction product and fromabout 0.8 to about 5.0 mols of an inorganic basic compound per mol ofphosphorus in said reaction product at a temperature in the range offrom about F. to about 400 F. in the presence of an alcohol-containingsolvent wherein the alcohol is an aliphatic alcohol boiling below about350 F., said inorganic basic compound being selected from the inorganicbasic compounds of alkali metals and the inorganic basic compounds ofalkaline earth metals and said alcohol-containing sol-vent providingfrom about 2 to about 15 mols of aliphatic alcohol per mol of inorganicbasic compound.

12. A process for producing new and useful oil-soluble detergentneutralized phosphorus sulfide-hydrocarbon reaction products, whichprocess comprises reacting a hydrolyzed phosphorus sulfide-hydrocarbonreaction product, said hydrolyzed product having been prepared byreacting a normally liquid hydrocarbon with from about 1% to about 50%phosphorus sulfide at a temperature in the range of from about 200 toabout 600 F. and hydrolyzing at a temperature in the range of from about200 to about 500 F., with from about 0.5 to about 2.5 mols of boric acidper mol of phosphorus in said reaction product, from about 4 to about 15parts by weight of petroleum sulfonic acid per part by Weight ofphosphorus in said reaction product and from about 1.5 to about 4.0 molsof an inorganic basic barium compound per mol of phosphorus in saidreaction product at a temperature in the range of from about 120 F. toabout 400 F. in the presence of an alcohol-containing reaction solventwherein the alcohol is an aliphatic alcohol having from 1 to 7 carbonatoms, said solvent being present in an amount sufficient to providefrom about 2 to about 15 mols of aliphatic alcohol per mol of saidbarium compound.

References Cited in the file of this patent UNITED STATES PATENTS OTHERREFERENCES Kalichevsky-Kobe: Petroleum Refining With Chemi- 15 cals,1956, Elsevier Publishing Co., New York, pp. 620- 639 pertinent.

1. AS A NEW COMPOSITION OF MATTER, AN OIL-SOLUBLE DETERGENT NEUTRALIZEDREACTION PRODUCT PREPARED BY THE PROCESS COMPRISING REACTING A NORMALLYLIQUID HYDROCARBON WITH FROM ABOUT 1% TO ABOUT 50% OF A PHOSPHOROUSSOLUFIDE AT A TEMPERATURE IN THE RANGE OF FROM ABOUT 200*F. TO TO ABOUT600*F., HYDROLYZING THE RESULTING REACTION PRODUCT AT A TEMPERATURE INTHE RANGE OF FROM ABOUT 200* F. TO ABOUT 500*F., REACTING THE RESULTINGHYDROLYZED REACTION PRODUCT WITH FROM ABOUT 0.1 TO ABOUT 5.0 MOLS OFBORIC ACID PER MOL OF PHOSPHORUS IN SAID REACTION PRODUCT, FROM ABOUT 1TO ABOUT 30 PARTS BY WEIGHT OF PETROLEUM SULFONIC ACID PER PART BYWEIGHT OF PHOSPHORUS IN SAID REACTION PRODUCT AND FROM ABOUT 0.8 TOABOUT 5.0 MOLS OF AN INORGANIC BASIC COMPOUND PER MOL OF PHOSPHORUS INSAID REACTION PRODUCT AT A TEMPERATURE IN THE RANGE OF FROM ABOUT 120*F.TO ABOUT 400*F. IN THE PRESENCE OF AN ALCOHOLCONTAINING SOLVENT WHEREINTHE ALCOHOL IS A ALIPHATIC ALCOHOL BOILING BELOW ABOUT 350*F., SAIDINORGANIC BASIC COMPOUND BEING SELECTED FROM THE INORGANIC BASICCOMPOUNDS OF ALKALI METALS AND THE INORGNIC BASIC COMPOUNDS OF ALKALINEEARTH METALS AND SAID ALCOHOL-CONTAINING SOLVENT PROVIDING FROM ABOUT 2TO ABOUT 15 MOL OF ALIPHATIC ALCOHOL PER MOL OF INORGANIC BASICCOMPOUND.